CN116726729A - In-situ MOF (metal oxide fiber) -type stereocomplex polylactic acid micro/nano fiber self-energized filter membrane and preparation method thereof - Google Patents
In-situ MOF (metal oxide fiber) -type stereocomplex polylactic acid micro/nano fiber self-energized filter membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides an in-situ MOF (metal oxide fiber) -type stereocomplex polylactic acid micro/nano fiber self-energized filter membrane and a preparation method thereof. The method comprises the following steps: the microwave assisted synthesis method and the template method are combined to prepare ZIF-8 nanocrystals with uniform morphology and stable size, and the ZIF-8 dispersion liquid and the L-polylactic acid (PLLA)/D-polylactic acid (PDLA) blending solution are co-spun by the electrospray-electrostatic spinning combined method to prepare the in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane. The prepared in-situ MOF-type three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane has adjustable bead and mesoporous morphology, and the ZIF-8 endowed high specific surface area and surface activity, so that the membrane has high filtration performance, excellent triboelectric output performance and good self-cleaning capability, and has wide application prospect in the fields of individual protection and intelligent monitoring.
Description
Technical Field
The invention belongs to the technical field of fiber filtering membranes, and particularly relates to an in-situ MOF (metal oxide fiber) three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane and a preparation method thereof.
Background
Atmospheric Particulate (PM) pollution has a significant impact on economy and public health. Since fine PM (aerodynamic diameter of 2.5 μm or less, i.e., PM 2.5) can carry a large amount of bacteria and viruses to permeate into the respiratory system of the human body and cause harm to the human body, an efficient and low-energy-consumption strategy is required to protect the public from serious PM pollution, and at the same time, in order to alleviate plastic pollution and microplastic hazard caused by the conventional filter materials, there is an increasing demand for degradable air filter materials for effectively removing PM. Polylactic acid (PLA) has no toxicity, high biocompatibility and complete biodegradability, so that the polylactic acid has wide application prospect in the field of air filtration.
However, the conventional polylactic acid fiber membranes have the following problems in practical use as air filtration membranes: (1) relatively low filtration efficiency; (2) poor self-cleaning ability; (3) triboelectric output performance is weaker.
Therefore, there is an urgent need for an improvement in polylactic acid fiber filtration membranes for better application to air filtration.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an in-situ MOF (metal oxide fiber) three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane and a preparation method thereof, which meet the requirements of a long-acting air filter membrane.
The specific technical scheme is as follows:
an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane is prepared from spinning solution A, spinning solution B and electrospray ZIF-8 stock solution; the average diameter of the nano-fibers of the filter membrane is 150-1000 nm, the average diameter of the micro-fibers is 1-10 mu m, the size of the beads is 1-20 mu m, the mesoporous size of the fiber surface is 50-500 nm, and the thickness of the fiber membrane is 20-600 mu m.
Further, the spinning solution A comprises a PLLA/PDLA blend, and the mass fraction of the PLLA/PDLA blend in the spinning solution A is 0.1-7wt%; the spinning solution B comprises a PLLA/PDLA blend, and the mass fraction of the PLLA/PDLA blend in the spinning solution A is 8-18 wt%.
The method for preparing the in-situ MOF stereocomplex polylactic acid micro/nano fiber self-energized filter membrane comprises the following steps:
s1, preparing ZIF-8 crystals: mixing 2-methylimidazole solution and zinc salt for microwave-assisted synthesis to prepare ZIF-8 dispersion, extracting and drying to obtain ZIF-8 crystals;
s2, preparing ZIF-8 electrospray stock solution: dispersing the ZIF-8 crystal obtained in the step S1 in a solvent, and adding a dispersing agent to obtain stable and uniform electrosprayed ZIF-8 stock solution;
s3, preparing an electrostatic spinning solution A: mixing PDLA and PLLA according to a certain mole ratio, and then dissolving the mixture in a mixed solvent consisting of a good solvent and a non-good solvent to prepare spinning solution A (low concentration);
s4, preparing an electrostatic spinning solution B: mixing PDLA and PLLA according to a certain mole ratio, and then dissolving the mixture in a mixed solvent consisting of a good solvent and a non-good solvent to prepare spinning solution B (high concentration);
s5, preparing an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane: and (3) preparing a fiber membrane by using the ZIF-8 electrospraying stock solution obtained in the step (S2) and the spinning solution B obtained in the step (S3) and using the spinning solution A, S to prepare a self-powered MOF-type stereocomplex polylactic acid micro/nano fiber filter membrane through a synchronous electrospraying/electrospinning method.
Further, at least one of water-soluble zinc salt zinc nitrate, zinc chloride, zinc sulfate and zinc acetate used in the step S1, wherein the concentration of the zinc salt is 0.01-5 mol/L, and the molar ratio of the 2-methylimidazole to the zinc salt is 40:1-1:40.
Further, in the step S1, the output power of the microwave reaction kettle is 100-1500W, the reaction temperature is 40-200 ℃, and the reaction time is 20-120 min.
Further, the dispersing agent used in the step S2 is at least one of polyvinylpyrrolidone, dodecyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the mass ratio of ZIF-8 to the dispersing agent is 1:10-1:1000.
Further, the solvent used in the step S2 is at least one of dimethylformamide, dichloromethane, chloroform, N-methylpyrrolidone, hexafluoroisopropanol, methanol, ethanol, isopropanol and glycerol, and the mass fraction of ZIF-8 in the dispersion liquid is 0.01-10wt%.
Further, the good solvent used in the step S3 is at least one of dichloromethane, chloroform, N-dimethylformamide, N-methylpyrrolidone, hexafluoroisopropanol, tetrahydrofuran and ethyl acetate, and the poor solvent is at least one of methanol, ethanol, isopropanol, glycerol, butanol, ethylene glycol and propylene glycol; the mole ratio of PDLA and PLLA in the spinning solution A is 1:0.1-1:20, the volumes of the non-good solvent and the good solvent are 1:1-1:10, and the mass fraction of the PLLA/PDLA blend in the spinning solution A is 0.1-7wt%.
Further, the good solvent used in the step S4 is at least one of dichloromethane, chloroform, N-dimethylformamide, N-methylpyrrolidone, hexafluoroisopropanol, tetrahydrofuran and ethyl acetate, and the poor solvent is at least one of methanol, ethanol, isopropanol, glycerol, butanol, ethylene glycol and propylene glycol; the mole ratio of PDLA and PLLA in the spinning solution B is 1:0.1-1:20, the volume ratio of the non-good solvent and the good solvent is 1:1-1:100, and the mass fraction of the PLLA/PDLA blend in the spinning solution B is 8-18 wt%.
Further, in the step S5, the diameter of the needle head of the electrostatic spinning needle is 0.06-1.54 mm, the voltage of an applied electrostatic field is 10-60 kV, the spinning temperature is 20-65 ℃, and the relative humidity of the environment is 25-85%.
Further, in the step S5, the consumption rate of the ZIF-8 electrospray stock solution is 0.1-10 mL/h, the consumption rate of the spinning solution A is 0.1-10 mL/h, the consumption rate of the spinning solution B is 0.1-10 mL/h, and the receiving distance is 10-30 cm.
Further, in the step S5, the average diameter of the fiber obtained from the spinning solution A is 150-1000 nm, and the average diameter of the fiber obtained from the spinning solution B is 1-10 μm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) In the preparation method of the in-situ MOF-type stereocomplex polylactic acid micro/nano fiber self-energized filter membrane, the stereocomplex polylactic acid is prepared by mixing and co-spinning the levorotatory polylactic acid (PLLA) and the dextrorotation polylactic acid (PDLA), the beta crystal content is improved, the triboelectric output performance is improved, and a micro/nano multi-stage structure is constructed by utilizing the concentration gradient difference of the PDLA/PLLA mixed solution, so that the morphology and the quantity of beads can be controllably adjusted. By constructing a ternary system of polymer-non-good solvent, the in-situ generation of the controllable mesoporous structure is realized under the induction of phase separation by the poor solvent.
(2) The in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane endows the fiber with high specific surface area and surface activity through a bead string/porous structure and the anchoring of ZIF-8 on the surface of the fiber, improves the filtering performance, reduces the air resistance, increases the friction contact area of the fiber and improves the friction output performance. Meanwhile, the bead structure and ZIF-8 are beneficial to constructing the super-hydrophobic surface, so that the fiber membrane has good self-cleaning capability.
(3) The specific surface area of the in-situ MOF stereocomplex polylactic acid micro/nano fiber self-energized filter membrane reaches 330.5-850.5m 2 And/g, PM0.3 filtering efficiency is 98.3-99.8%, PM2.5 filtering efficiency is 98.8-99.9%, air resistance is lower than 100Pa when flow is 85L/min, dielectric constant is high (0.65-0.98F/m), and output performance is high (output voltage is as high as 25.6V).
(4) The in-situ MOF-type three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane has high filtering performance, excellent triboelectric output performance and good self-cleaning capability, and has wide application prospect in the fields of individual protection and intelligent monitoring.
Drawings
FIG. 1 is a route diagram of a preparation method of the present invention;
FIG. 2 is a scanning electron micrograph of the in situ MOF-stereocomplex polylactic acid micro/nano-fiber self-energized filter membrane obtained in example 2;
FIG. 3 is a graph showing water contact angles of polylactic acid fiber membranes obtained in example 2 (a) and comparative example 2 (b);
FIG. 4 is a graph showing the self-cleaning performance of the polylactic acid micro/nano-fiber self-energized filter membrane obtained in example 2 before (a) and after (b, c) testing.
Detailed Description
The following detailed description of the present invention is provided merely for further explanation of the invention and is not intended to limit the invention in any way as claimed in figures 1-4.
Friction nano-generators (TENGs) are an emerging energy harvesting device that can efficiently harvest different forms of low frequency mechanical energy. Studies have shown that TENG can produce high open-circuit voltages of tens to hundreds of volts and has no ozone emissions and great potential for air pollution control. TENG may filter PM by the generated triboelectric charge, known as triboelectric air dust removal technology. The TENG is assembled into a filter, which can be continuously provided with an electrostatic charge to adsorb small particles with higher efficiency. Furthermore, TENG-based wearable electronic devices have been applied in medical monitoring systems to monitor respiratory status of infected patients, obtain a large amount of physiological related information and possibly disease cues.
The metal-organic framework (MOF) is formed by coordination combination of central metal ions or metal clusters and organic ligands, and is a novel nano-porous material with a repeated structure and an ordered space. Compared with the traditional porous material, the MOFs have the characteristics of higher specific surface area and porosity, uniform structure, multiple adsorption sites, controllable size, adjustable aperture and the like, and can be chemically modified without changing the topological structure, so that the MOFs are used for preparing triboelectric nano generators and expanding triboelectric series.
The preparation method combines a microwave-assisted synthesis method and a template method, and optimizes the preparation conditions of the ZIF-8 nanocrystals. The stereocomplex polylactic acid is prepared by mixing and co-spinning the L-polylactic acid (PLLA) and the D-polylactic acid (PDLA), so that the content of the electroactive beta-crystal is increased, and the triboelectric output performance is improved. And constructing a micro/nano multi-stage structure by utilizing the concentration gradient difference of the PDLA/PLLA mixed solution, so as to realize controllable adjustment of the morphology and the quantity of the beads. By constructing a ternary system of polymer-non-good solvent, the in-situ generation of the controllable mesoporous structure is realized under the induction of phase separation by the poor solvent. The ZIF-8 with high dielectric and high specific surface area is anchored on the surface of the fiber by an electric spraying method, and the specific surface area and the surface activity are increased, so that the fiber membrane has high filtration efficiency, excellent triboelectric output performance and good self-cleaning function.
Example 1
The preparation method of the in-situ MOF stereocomplex polylactic acid micro/nano fiber self-energized filter membrane comprises the following steps:
s1, preparing ZIF-8 crystals: mixing 2-methylimidazole solution and zinc acetate (the mass ratio of the 2-methylimidazole solution to the zinc acetate is 40:1), and then performing microwave-assisted synthesis on ZIF-8 crystals (the output power of a microwave reaction kettle is 1500W, the reaction temperature is 200 ℃, and the reaction time is 20 min);
s2, preparing ZIF-8 electrospray stock solution: dispersing ZIF-8 crystals in dimethylformamide, and then adding a polyvinylpyrrolidone dispersing agent to obtain ZIF-8 electrospray stock solution (the mass ratio of ZIF-8 to the dispersing agent is 1:10, and the mass fraction of ZIF-8 in the dispersing solution is 10wt%);
s3, preparing electrostatic spinning solution A: PDLA and PLLA were mixed in a molar ratio of 1:10 as a matrix polymer and dissolved in a mixed solvent consisting of methylene chloride and ethanol (the volume ratio of methylene chloride to ethanol was 1:10) to prepare a dope A having a concentration of 7wt%;
s4, preparing electrostatic spinning solution B, mixing PDLA and PLLA according to a molar ratio of 1:15 to obtain a matrix polymer, and dissolving the matrix polymer in a mixed solvent consisting of dimethylformamide and ethanol (the volume ratio of the dimethylformamide to the ethanol is 1:100) to prepare spinning solution B with the concentration of 18 wt%;
s5, preparing an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane: and (3) carrying out electrospraying/electrospinning (the electrospraying voltage is 20kV, the spinning voltage is 60kV, the spinning temperature is 40 ℃, the environment relative humidity is 85%, and the receiving distance is 17 cm) on the ZIF-8 electrospraying stock solution (4 mL, the needle diameter is 0.84mm, the consumption rate is 0.8 mL/h) obtained in the S12, the spinning solution A (4 mL, the needle diameter is 0.84mm, the consumption rate is 0.8 mL/h) obtained in the S13 and the S14 spinning solution B (4 mL, the needle diameter is 0.84mm, the consumption rate of B is 0.8 mL/h) to obtain the in-situ MOF-type three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane, and annealing at 40 ℃ for 8 hours.
The average diameter of the nanofibers of the obtained filter membrane is 500nm, the average diameter of the microfibers is 2 mu m, the average pore diameter is 58nm, the average bead size is 10 mu m, and the thickness of the fiber membrane is 100 mu m.
Example 2
The preparation method of the in-situ MOF stereocomplex polylactic acid micro/nano fiber self-energized filter membrane comprises the following steps:
s1, preparing ZIF-8 crystals: mixing 2-methylimidazole solution and high zinc sulfate (the mass ratio of the 2-methylimidazole solution to the zinc nitrate is 1:1), and then performing microwave-assisted synthesis on ZIF-8 (the output power of a microwave reaction kettle is 800W, the reaction temperature is 160 ℃, and the reaction time is 40 min);
s2, preparing ZIF-8 electrospray stock solution: dissolving ZIF-8 in dichloromethane, and then adding dodecyl trimethyl ammonium bromide dispersant to obtain ZIF-8 electrospray stock solution (the mass ratio of ZIF-8 to dispersant is 1:1000, and the mass fraction of ZIF-8 in the dispersion is 0.01 wt%);
s3, preparing electrostatic spinning solution A: PDLA and PLLA are mixed according to the mol ratio of 1:7 to be used as matrix polymer, and the matrix polymer is dissolved in a mixed solvent consisting of chloroform and methanol (the volume ratio of the chloroform to the methanol is 1:10) to prepare spinning solution A with the concentration of 1 wt%;
s4, preparing electrostatic spinning solution B, mixing PDLA and PLLA according to a molar ratio of 1:14 to obtain a matrix polymer, and dissolving the matrix polymer in a mixed solvent consisting of N-methylpyrrolidone and glycerol (the volume ratio of the N-methylpyrrolidone to the glycerol is 1:1) to prepare spinning solution B with the concentration of 8 wt%;
s5, preparing an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane: the ZIF-8 electrospun stock solution (8 mL, needle diameter of 0.51mm, consumption rate of 0.8 mL/h) obtained in S22, the spinning solution A (10 mL, needle diameter of 0.21mm, consumption rate of 1.0 mL/h) obtained in S23 and the spinning solution B (10 mL, needle diameter of 0.34mm, consumption rate of 1.0 mL/h) obtained in S24 were electrosprayed/electrospun (electrosprayed voltage of 10kV, electrosprayed voltage of 30kV, spinning temperature of 40 ℃, environmental relative humidity of 85%, receiving distance of 15 cm) and annealed at 40 ℃ for 12h to prepare the in situ MOF-stereocomplex polylactic acid micro/nanofiber self-energized filter membrane.
The average diameter of the nanofibers of the obtained filter membrane is 350nm, the average diameter of the microfibers is 5.6 μm, the average pore diameter is 128nm, the average bead size is 8.5 μm, and the thickness of the fiber membrane is 200 μm.
Example 3
The preparation method of the in-situ MOF stereocomplex polylactic acid micro/nano fiber self-energized filter membrane comprises the following steps:
s1, preparing ZIF-8 crystals: mixing 2-methylimidazole solution and zinc fluoride (the mass ratio of the 2-methylimidazole solution to the zinc fluoride is 8:1), and then performing microwave-assisted synthesis on ZIF-8 (the output power of a microwave reaction kettle is 1000W, the reaction temperature is 100 ℃, and the reaction time is 30 min);
s2, preparing ZIF-8 electrospray stock solution: dissolving ZIF-8 in chloroform, and then adding a sodium dodecyl sulfate dispersing agent to obtain ZIF-8 electrospray stock solution (the mass ratio of ZIF-8 to the dispersing agent is 1:40, and the mass fraction of ZIF-8 in the solution is 0.75wt%);
s3, preparing electrostatic spinning solution A: PDLA and PLLA are mixed according to the mol ratio of 1:6 to be used as matrix polymer, and the matrix polymer is dissolved in a mixed solvent consisting of dimethylformamide and isopropanol (the volume ratio of the dimethylformamide to the isopropanol is 1:4) to prepare spinning solution A with the concentration of 5 wt%;
s4, preparing electrostatic spinning solution B, mixing PDLA and PLLA according to a molar ratio of 1:12 to obtain a matrix polymer, and dissolving the matrix polymer in a mixed solvent consisting of ethyl acetate and propylene glycol (the volume ratio of the ethyl acetate to the propylene glycol is 1:7) to prepare spinning solution B with the concentration of 15 wt%;
s35, preparing an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane: and (3) carrying out electrospraying/electrospinning (the electrospraying/electrospinning voltage is 25kV, the spinning temperature is 40 ℃, the relative humidity of the environment is 40%, and the receiving distance is 15 cm) on the ZIF-8 electrospraying stock solution (18 mL, the diameter of a needle is 0.21mm, the consumption rate is 1.2 mL/h) obtained in the S32, the spinning solution A (12 mL, the diameter of the needle is 0.21mm, the consumption rate is 1.0 mL/h) obtained in the S33 and the spinning solution B (12 mL, the diameter of the needle is 0.84mm, the consumption rate of B is 1.0 mL/h) obtained in the S34, and annealing at 40 ℃ for 24 hours to prepare the in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane.
The average diameter of the nanofiber of the obtained filter membrane is 800nm, the average diameter of the microfiber is 5 mu m, the average pore diameter is 35nm, the average bead size is 11.5 mu m, and the thickness of the fiber membrane is 420 mu m.
Example 4
An in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane and a preparation method thereof, comprising the following steps:
s1, preparing ZIF-8 crystals: mixing 2-methylimidazole solution and zinc iodide (the mass ratio of the 2-methylimidazole solution to the zinc iodide is 20:1), and then performing microwave-assisted synthesis on ZIF-8 crystals (the output power of a microwave reaction kettle is 500W, the reaction temperature is 120 ℃, and the reaction time is 120 min);
s2, preparing ZIF-8 electrospray stock solution: dissolving ZIF-8 in N-methylpyrrolidone, and then adding a sodium dodecyl benzene sulfonate dispersing agent to obtain ZIF-8 electrospray stock solution (the mass ratio of ZIF-8 to the dispersing agent is 1:10, and the mass of ZIF-8 in the solution is 5 wt%);
s3, preparing electrostatic spinning solution A, mixing PDLA and PLLA according to a molar ratio of 1:5 to obtain a matrix polymer, and dissolving the matrix polymer in a mixed solvent consisting of chloroform and n-butanol (the volume ratio of the chloroform to the n-butanol is 1:5) to prepare the spinning solution A with the concentration of 15 wt%.
S4, preparing electrostatic spinning solution B, mixing PDLA and PLLA according to a molar ratio of 1:10 to obtain a matrix polymer, and dissolving the matrix polymer in a mixed solvent consisting of tetrahydrofuran and ethylene glycol (the volume ratio of the tetrahydrofuran to the ethylene glycol is 0.1:5) to prepare spinning solution B with the concentration of 25 wt%;
s5, preparing an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane: and (3) electrospraying/electrospinning (the electrospraying/electrospinning voltage is 45kV, the spinning temperature is 60 ℃, the ambient relative humidity is 45%, the receiving distance is 15 cm) is carried out on the ZIF-8 electrospraying stock solution (18 mL, the needle diameter is 0.34mm, the consumption rate is 1.5 mL/h) obtained in the S42, the spinning solution A (12 mL, the needle diameter is 0.34mm, the consumption rate is 2 mL/h) obtained in the S43 and the spinning solution B (12 mL, the needle diameter is 0.84mm, the consumption rate of B is 2 mL/h) obtained in the S44, and annealing treatment is carried out at 60 ℃ for 12 hours to prepare the in-situ MOF stereocomplex polylactic acid micro/nano fiber self-energized filter membrane.
The average diameter of the nanofiber of the obtained filter membrane is 800nm, the average diameter of the microfiber is 5 mu m, the average pore diameter is 35nm, the average bead size is 12.4 mu m, and the thickness of the fiber membrane is 400 mu m.
Comparative example 1
The method of example 1 was essentially used to prepare a stereocomplex polylactic acid micro/nanofiber membrane, except that ZIF-8 was not added in this example, specifically, PDLA and PLLA were prepared in a 1:10 mol% of the polymer was mixed as a matrix polymer, and dissolved in a mixed solvent composed of methylene chloride and ethanol (the volume ratio of methylene chloride and ethanol was 1:0.1) to prepare a dope A having a concentration of 7wt%. PDLA and PLLA were mixed in a molar ratio of 1:15 to prepare a dope B having a concentration of 18wt% by dissolving the polymer in a mixed solvent comprising dimethylformamide and ethanol (the volume ratio of dimethylformamide to ethanol was 1:0.1). Subsequently, the obtained spinning solution A (4 mL, needle diameter of 0.84mm, consumption rate of 0.8 mL/h) and spinning solution B (4 mL, needle diameter of 0.84mm, consumption rate of 0.8 mL/h) were subjected to multi-needle electrostatic spinning (electrospray voltage of 20kV, spinning voltage of 60kV, spinning temperature of 40 ℃, ambient relative humidity of 85%, receiving distance of 17 cm), and annealed at 40℃for 8 hours to prepare a stereocomplex polylactic acid micro/nano-fiber filter membrane.
The average diameter of the nanofiber of the obtained filter membrane is 654nm, the average diameter of the microfiber is 5.3 mu m, the average pore diameter is 158nm, the average bead size is 8.5 mu m, and the thickness of the fiber membrane is 100 mu m.
Comparative example 2
The method of example 2 was basically used to prepare a stereocomplex polylactic acid micro/nano-fiber film, except that the ZIF-8 crystals prepared in example 2 were dried by high-speed centrifugation and then were used, and ZIF-8 crystal powder was added to the spinning solution a and the spinning solution B, respectively, to perform electrospinning. Specifically, PDLA and PLLA were mixed in a molar ratio of 1:7 as a matrix polymer, and dissolved in a mixed solvent composed of chloroform and methanol (the volume ratio of chloroform to methanol was 1:10) to prepare a dope A having a concentration of 1 wt%. PDLA and PLLA were mixed in a molar ratio of 1:14 to prepare a matrix polymer, which was dissolved in a mixed solvent consisting of N-methylpyrrolidone and glycerol (the volume ratio of N-methylpyrrolidone to glycerol was 1:1) to prepare a dope B having a concentration of 8wt%.
Subsequently, ZIF-8 crystal powder is respectively added into the spinning solution A and the spinning solution B (the mass fractions are respectively 10 percent and 15 percent) to carry out multi-needle electrostatic spinning, and the spinning parameters are respectively set as follows: spinning solution A (10 mL, needle diameter 0.21mm, consumption rate 1.0 mL/h), spinning solution B (10 mL, needle diameter 0.34mm, consumption rate 1.0 mL/h) was subjected to multi-needle electrospinning (electrospinning voltage: 30kV, spinning temperature: 40 ℃, ambient relative humidity: 85%, receiving distance: 15 cm), and annealing at 40℃for 12 hours to prepare a stereocomplex polylactic acid micro/nanofiber membrane.
The average diameter of the nanofibers of the obtained filter membrane was 350nm, the average diameter of the microfibers was 5 μm, the average pore diameter was 156nm, and the thickness of the fiber membrane was 380. Mu.m.
Structural characterization and performance testing
Tensile property test: the resulting nanofiber membrane was cut to obtain a tensile bar, and the tensile properties of the composite membrane were tested according to the tensile properties test standard of plastics in ASTM D638-2003 of the american society for testing and materials using a universal stretcher (model 4403, sensor 100N) from Instron company, usa. At least 3 parallel test samples were secured for each group and the results averaged.
Surface potential test: the nanofiber membrane was tested for surface potential using a noncontact electrostatic meter (VM 54XQS, quatek company, usa) at a test height of 2cm and constant temperature and humidity of 25 ℃ and 45%, and 20 data points were randomly collected for each sample and averaged.
Filtration performance test: an LZC-K automatic filter material tester (Suzhou Huada instrument)Test fiber film (area 113.04 cm) 2 ) The air filtration performance of the device is set to be 85L/min, and the particle size range of NaCl atomized crystals generated by the aerosol generator is 0.1-10 mu m. At least 3 different positions were tested for each set of fibrous membranes and the results averaged.
Water contact angle test: the Contact Angle (CA) was measured with a JC2000D1 contact angle system (Shanghai Chen) with 2. Mu.L drops. The average CA values were obtained by testing three different regions of the sample.
Self-cleaning performance test: the fiber membrane is placed on the glass sloping plate, pollutant particles (indoor dust) are scattered on the surface of the fiber membrane, so that the surface of the fiber membrane is polluted by the dust, then high-speed shearing is realized through air flow of the air pump (water drops are dropped on the surface of the fiber membrane through the plastic dropper) to take away the particles on the surface of the fiber membrane, and the membrane is cleaned again and reused.
The results are shown in tables 1-3, and the results of the tests of specific surface area, dielectric constant, surface potential, mechanical property, filtration property, output property and water contact angle of the in-situ MOF-type stereocomplex polylactic acid micro/nano fiber self-energized filter membrane obtained in the examples and the comparative examples are respectively compared in tables 1, 2 and 3.
TABLE 1 in situ MOF-based stereocomplex polylactic acid micro/nano fiber self-energized filter membrane dielectric constant and surface potential test results
In Table 1, examples 1 to 4 exhibited a relatively high specific surface area due to the anchoring of ZIF-8 to the fiber surface, and examples 1 to 4 and comparative example 2 each exhibited extremely high surface potentials (8.5 to 14.8 kV), and the surface potentials of the filter membranes in examples 1 to 4 hardly decayed with time, confirming extremely high long-term stability. In table 1, the significant improvement in dielectric constant of examples 1-4 over comparative example 1, the high specific surface area, high surface potential, high dielectric constant and enhanced nanofiber confinement properties make microporous nanofibers an ideal platform for molecular sieving and adsorptive separation, generally exhibiting a stronger loading capacity and lower air resistance.
TABLE 2 in situ MOF-based stereocomplex polylactic acid micro/nano fiber self-energized filter membrane specific surface area, mechanical property, filtration performance test results
In Table 2, the filtration efficiencies of examples 1 to 4 for PM0.3 and PM2.5 were 98% or more. Comparative example 1 shows that the filtration efficiency of the fiber membrane for PM0.3 and PM2.5 is lower than that for high potential, 70.3% for PM0.3 and 72.4% for PM2.5 at lower surface potential.
In Table 2, the breaking strength of the fiber films in examples 1 to 4 was between 19.6 and 33.5 MPa, which is much higher than that of comparative examples 1 to 2. The ZIF-8 fills the vacancies on the surface of the fiber, reduces the defects on the surface of the fiber and improves the breaking strength of the fiber, but with the increase of the ZIF-8 content, the breaking strength of the fiber film is increased and then reduced, mainly because the ZIF-8 can be used as a nucleation point to promote the crystal growth in the process of three-dimensional compounding, the crystallinity of the polylactic acid fiber is improved, the physical crosslinking point in the molecule is increased, and the mechanical property is improved. However, when the ZIF-8 content is too large, the stress concentration points of the fibers are increased, and the heterogeneous nucleation is weakened, so that the breaking strength is reduced, and the addition of a proper amount of ZIF-8 is beneficial to improving the strength of the nanofiber membrane. TABLE 3 results of in situ MOF-stereocomplex polylactic acid micro/nano fiber self-energized filter membrane output performance and water contact angle test
In Table 3, the triboelectric output performance of examples 1-4 was 16.9-25.6V, which is much higher than that of comparative examples 1-2. This is mainly because the introduction of ZIF-8 between the fibers increases the friction area of the fibers, and because ZIF-8 has higher electron conversion capability, the addition of beads/porous structure improves the stacking mode of the fibers, increases the fiber-to-fiber contact area (as shown in fig. 2), and increases the output voltage of the fiber membrane. Meanwhile, the improvement of the water contact angle is mainly due to the synergistic effect of the hydrophobic ZIF-8 and the bead structure, so that the fiber membrane has self-cleaning capability (shown in figures 3 and 4).
Therefore, the technical scheme provided by the invention enables the in-situ MOF-type three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane to have excellent filtering performance, triboelectric output performance and self-cleaning capability. These are likely to benefit from: (1) The fiber forms a bead structure by utilizing the solubility gradient difference of the solution, a 'poor solvent-good solvent-polymer' ternary system is constructed, and the surface of the three-dimensional composite polylactic acid fiber is in situ generated into a controllable mesoporous structure by the principle of phase separation induced by the poor solvent. The bead/mesoporous structure improves the fiber stacking mode, reduces the air resistance, provides more binding sites for ZIF-8 on the surface of the fiber, increases the specific surface area and the surface activity of the fiber, and enhances the adsorption capacity to particulate matters; (2) The fiber forms a super-hydrophobic surface by the synergistic effect of the bead structure and the ZIF-8 uniformly attached to the surface of the fiber, so that the adhesive force of dirt is greatly reduced, and the dirt can be automatically separated from the surface of the ZIF-8 when the dirt is acted by mechanical forces such as airflow, water and the like, thereby realizing self cleaning; (3) Because ZIF-8 has larger specific surface and friction contact area and higher electron exchange capacity, the triboelectric output performance of the fiber membrane is obviously improved; (4) The stereocomplex polylactic acid obtains higher crystallinity and regularly arranged chain conformation through the interaction of hydrogen bonds among chains, so that the mechanical property and the filtering property of the fiber membrane are enhanced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. An in-situ MOF (metal oxide fiber) stereocomplex polylactic acid micro/nano fiber self-energized filter membrane is characterized by being prepared from spinning solution A, spinning solution B and electrospray ZIF-8 stock solution; the average diameter of the nano-fibers of the filter membrane is 150-1000 nm, the average diameter of the micro-fibers is 1-10 mu m, the size of the beads is 1-20 mu m, the mesoporous size of the fiber surface is 50-500 nm, and the thickness of the fiber membrane is 20-600 mu m.
2. The in-situ MOF-oriented stereocomplex polylactic acid micro/nano fiber self-energized filter membrane according to claim 1, wherein the spinning solution A comprises a PLLA/PDLA blend, and the mass fraction of the PLLA/PDLA blend in the spinning solution A is 0.1-7wt%; the spinning solution B comprises a PLLA/PDLA blend, and the mass fraction of the PLLA/PDLA blend in the spinning solution A is 8-18 wt%.
3. A method for preparing the in situ MOF-like stereocomplex polylactic acid micro/nano fiber self-energized filter membrane according to claim 1 or 2, comprising the steps of:
s1, preparing ZIF-8 crystals: mixing 2-methylimidazole solution and zinc salt for microwave-assisted synthesis to prepare ZIF-8 dispersion, extracting and drying to obtain ZIF-8 crystals;
s2, preparing ZIF-8 electrospray stock solution: dispersing the ZIF-8 crystal obtained in the step S1 in a solvent, and adding a dispersing agent to obtain stable and uniform electrosprayed ZIF-8 stock solution;
s3, preparing an electrostatic spinning solution A: mixing PDLA and PLLA according to a certain molar ratio, and then dissolving the mixture in a mixed solvent consisting of a good solvent and a non-good solvent to prepare spinning solution A;
s4, preparing an electrostatic spinning solution B: mixing PDLA and PLLA according to a certain molar ratio, and then dissolving the mixture in a mixed solvent consisting of a good solvent and a non-good solvent to prepare spinning solution B;
s5, preparing an in-situ MOF three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane: and (3) preparing a fiber membrane by using the ZIF-8 electrospraying stock solution obtained in the step (S2) and the spinning solution B obtained in the step (S3) and using the spinning solution A, S to prepare a self-powered MOF-type stereocomplex polylactic acid micro/nano fiber filter membrane through a synchronous electrospraying/electrospinning method.
4. The method for preparing the self-energized membrane of the in-situ MOF-functionalized stereocomplex polylactic acid micro/nano fiber, according to claim 3, wherein the concentration of zinc salt is 0.01-5 mol/L, and the molar ratio of 2-methylimidazole to zinc salt is 40:1-1:40.
5. The method for preparing the in-situ MOF-enhanced stereocomplex polylactic acid micro/nano fiber self-energized filter membrane according to claim 3, wherein the output power of the microwave reaction kettle in the step S1 is 100-1500W, the reaction temperature is 40-200 ℃, and the reaction time is 20-120 min.
6. The method for preparing the self-energized membrane of the in-situ MOF-stereocomplex polylactic acid micro/nano fiber according to claim 3, wherein the dispersing agent used in the step S2 is at least one of polyvinylpyrrolidone, dodecyl trimethyl ammonium bromide, dodecyl sodium sulfate and dodecyl sodium benzenesulfonate, and the mass ratio of ZIF-8 to the dispersing agent is 1:10-1:1000.
7. The method for preparing the self-energized membrane of in-situ MOF-stereocomplex polylactic acid micro/nano fiber as set forth in claim 3, wherein the solvent used in the step S2 is at least one of dimethylformamide, dichloromethane, chloroform, N-methylpyrrolidone, hexafluoroisopropanol, methanol, ethanol, isopropanol and glycerol, and the mass fraction of ZIF-8 in the dispersion is 0.01-10wt%.
8. The method of self-energized membrane filtration of in situ MOF stereocomplex polylactic acid micro/nano fiber according to claim 3, wherein the good solvent used in step S3 is at least one of dichloromethane, chloroform, N-dimethylformamide, N-methylpyrrolidone, hexafluoroisopropanol, tetrahydrofuran and ethyl acetate, and the poor solvent is at least one of methanol, ethanol, isopropanol, glycerol, butanol, ethylene glycol and propylene glycol; the mole ratio of PDLA and PLLA in the spinning solution A is 1:0.1-1:20, the volumes of the non-good solvent and the good solvent are 1:1-1:10, and the mass fraction of the PLLA/PDLA blend in the spinning solution A is 0.1-7wt%.
9. The method of self-energized membrane filtration of in situ MOF stereocomplex polylactic acid micro/nano fiber according to claim 3, wherein the good solvent used in step S4 is at least one of dichloromethane, chloroform, N-dimethylformamide, N-methylpyrrolidone, hexafluoroisopropanol, tetrahydrofuran and ethyl acetate, and the poor solvent is at least one of methanol, ethanol, isopropanol, glycerol, butanol, ethylene glycol and propylene glycol; the mole ratio of PDLA and PLLA in the spinning solution B is 1:0.1-1:20, the volume ratio of the non-good solvent and the good solvent is 1:1-1:100, and the mass fraction of the PLLA/PDLA blend in the spinning solution B is 8-18 wt%.
10. The method for preparing the in-situ MOF-formed three-dimensional composite polylactic acid micro/nano fiber self-energized filter membrane according to claim 3, wherein the diameter of the needle head of the electrostatic spinning needle in the step S5 is 0.06-1.54 mm, the voltage of an applied electrostatic field is 10-60 kV, the spinning temperature is 20-65 ℃, and the relative humidity of the environment is 25-85%; in the step S5, the consumption rate of the ZIF-8 electrospray stock solution is 0.1-10 mL/h, the consumption rate of the spinning solution A is 0.1-10 mL/h, the consumption rate of the spinning solution B is 0.1-10 mL/h, and the receiving distance is 10-30 cm.
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